Our invention is directed to (i) an emulsifier-free, single phase, nonporous, continuous, permeable polymeric film having a substantially uniform thickness, having entrapped and dissolved therein a fragrance material which is capable of evolving from the film into the environment proximate the film by means of molecular diffusion in a sustained and controlled release manner, as well as (ii) a process for using such polymeric film in order to impart a fragrance into the environment above the unobstructed outer surface of the film when the film is coated on the surface of a solid or semi-solid support, e.g., a woven or non-woven fabric substrate, a solid surface or the human epidermis.
Controlled release fragrance compositions traditionally required prepackaging of encapsulated fragrances into the final product, for example, a coacervation, encapsulation system composed of fragrance encapsulated in a gelatin-gum arabic shell.
Control release systems using film forming polymers have been previously attempted. Thus, Japanese Published Patent Application J9 0057-428 abstracted as follows:
NIEK-D23 87-183168/26=J90057-428-B PA1 Prepn. of long-lasting fragrance--contg. hydroxypropyl:cellulose, ethanol and/or methanol soln. and vinyl pyrrolidone PA1 NIPPON EKISHO KK 13.11.85-JP-262894 PA1 A97+P34 (04.12.90)*J62114909-A A61k-07/46+A611-09/01 13.11.85 as 252894 (RP) PA1 1-30 wt % of hydroxypropylcellose is added to the ethanol or methanol soln. of 1-60 wt % polyvinyl pyrrolidone. Then 1-60 wt % of fragrance material is added and mixed. PA1 AVANTAGE--Long lasting fragrance is obtd. when applied to the film or paper. Polyvinyl pyrrolidone covers the fragrance material contained and prevents its loss. (J62114909-A) (3pp) PA1 "1. A perfuming composition with deodorant or antiperspirant action for use in personal care, characterised in that it contains, in addition to an active deodorant or antiperspirant base, a perfuming base, either in the form of an aqueous emulsion, or in microencapsulated form, the said perfuming base being combined with PA1 (a) at least one solvent; PA1 (b) at least one resin; PA1 (c) at least one colorant; and PA1 (D) at least one liquid perfume PA1 (i) capable of evolving from within the polymeric film through said first laminar polymer surface into the environment proximate to and above said first laminar polymer surface by means of substantially steady state molecular diffusion at a substantially constant permeation rate of from about 1.times.10.sup.-7 up to about 0.1 mg-mm/cm.sup.2 -min in a sustained and controlled release manner; and PA1 (ii) substantially incapable of permeating that portion of said second laminar polymer surface which is juxtaposed with the surface of said planar solid or semi-solid support (e.g., the epidermis) PA1 (a) a first permeation region proximate and immediately adjacent to said first laminar polymer surface; and PA1 (b) a second reservoir region proximate and immediately adjacent to said second laminar polymer surface, PA1 (i) a water-soluble or water-swellable polymer; PA1 (ii) a fragrance material; PA1 (iii) water; and PA1 (iv) a gelling agent composition comprising at least one gelling agent, PA1 (i) a first laminar polymeric-gel surface; and PA1 (ii) a second laminar polymeric-gel surface, PA1 (i) molecules of at least one fragrance substance in an initial weight ratio of fragrance:polymeric gel of from about 0.01:20 up to about 50:0.01; and PA1 (ii) water molecules in an initial weight ratio of water:polymeric gel of from about 1:500 up to about 500:1, PA1 (a) capable of evolving from within the polymeric gel film through said first laminar polymeric-gel surface into the environment proximate said first laminar polymeric-gel surface by means of molecular diffusion at a permeation rate of from about 1.times.10.sup.-7 up to about 0.1 mg-mm/cm.sup.2 -min in a substantially controlled release manner in accordance with Fick's second law; and PA1 (b) substantially incapable of permeating that portion of said second laminar polymeric-gel surface which is juxtaposed with said surface of said planar solid or semi-solid support (e.g., a woven or non-woven fabric, a solid surface or the human epidermis) PA1 (i) combining a composition comprising a solvent consisting of water, ethanol or mixtures of water and ethanol with a solvent-soluble polymer solute to form a polymer solution; then PA1 (ii) dissolving a soluble fragrance substance in said polymer solution in order to form an aromatized polymer solution; and then PA1 (iii) uniformly applying said aromatized polymer solution to said substantially planar surface of said solid or semi-solid support (e.g., a woven or non-woven fabric, a solid surface or the human epidermis), PA1 (i) dissolving a quantity of Q moles of solute polymer in V liters of solvent to form a polymer solution of concentration molar Q/V; PA1 (ii) dissolving F moles of fragrance substance in said solution of polymer to form a fragrance solution of concentration of F/V molar; PA1 (iii) uniformly applying said solution to said surface of said solid support (for example, by means of spraying through a pressure nozzle the solution onto a woven fabric such as woven cotton or onto a non-woven fabric composed of polypropylene), PA1 (i) dissolving a quantity of from about 0.01 up to about 20 parts by weight of a solvent-soluble polymer solute in from about 30 up to about 99.98 parts by weight of a solvent/base composition in order to form a polymer-base composition solution containing from about 0.01% up to about 67% polymer; PA1 (ii) adding a gelling agent to the polymer-base composition solution in order to form a polymer-base solution-gelling agent composition; PA1 (iii) dissolving from about 0.01 up to about 50 parts by weight of a soluble fragrance substance in said polymer-base solution-gelling agent composition in order to form an aromatized polymer-base solution-gelling agent composition; and PA1 (iv) uniformly applying said aromatized polymer-base solution-gelling agent composition to said substantially planar surface of said solid or semi-solid support (e.g., a woven or non-woven fabric, a solid surface or the human epidermis), whereby a single-phase, nonporous, continuous, permeable polymeric-gel film having a thickness of from about 1 micron up to about 150 microns, having dissolved therein molecules of said fragrance substance capable of evolving from said film into the environment proximate to the unobstructed outer surface of said film by means of molecular diffusion from about 1.times.10.sup.-7 up to about 0.1 mg-mm/cm.sup.2 -min in a sustained and controlled release manner is formed. PA1 (i) dissolving the solvent-soluble polymer in a solvent such as water, ethanol or mixtures of water and ethanol; PA1 (ii) mixing the resulting polymer solution with a base containing a substantial amount of propylene glycol and/or polypropylene glycol to form the polymer solution-base mixture; PA1 (iii) feeding the resulting polymer solution-base mixture; PA1 (iv) adding a gelling agent to the resulting mixture; and PA1 (v) adding an aromatizing agent to the resulting mixture to form an aromatized polymer solution-base-gelling agent mixture. PA1 (i) LUVISKOL.RTM. VA 55E having the structure: ##STR1## PA1 wherein n is an integer of from about 10 up to about 50 and m is an integer of from about 10 up to about 50; PA1 (ii) ULTRAHOLD.RTM. 8 having the structure: ##STR2## PA1 wherein each of x, y and z are integers in the range of from about 10 up to about 50; PA1 (iii) LUVIQUAT.RTM. FC or LUVIQUAT.RTM. having the structure: ##STR3## PA1 wherein teach of x and y are integers in the range of from about 10 up to about 50; PA1 (iv) ADVANTAGE PLUS.RTM. having the structure: ##STR4## PA1 wherein each of x, y and z are integers in the range of from about 10 up to about 50; PA1 (v) GAFQUAT.RTM. 734N or GAFQUAT.RTM. 755N (trademarks of International Chemical Specialties, Inc.) having the structure; ##STR5## PA1 wherein m is an integer of from about 5 up to about 30; PA1 (vi) DIAFORMERS.RTM. having the structure: ##STR6## PA1 wherein each of m and n are integers of from about 10 up to about 40; PA1 (vii) GAFQUAT.RTM. HS-100 having the structure: ##STR7## PA1 wherein each of x and y are integers of from about 10 up to about 20 (a trademark of International Chemical Specialties, Inc.); and PA1 (viii) OMNIREZ.RTM. 2000 and GANTREZ.RTM. A-425 having the structure: ##STR8## PA1 wherein x is an integer of from about 5 up to about 30 (trademarks of International Chemical Specialties, Inc.). PA1 (a) with respect to the bottom note components, the vapor pressure range should be from about 0.0001 mm/Hg up to about 0.009 mm/Hg at 25.degree. C.; PA1 (b) with respect to the middle note components, the vapor pressure range of the middle note components should be from 0.01 mm/Hg up to 0.09 mm/Hg at 25.degree. C.; and PA1 (c) with respect to the top note components, the vapor pressure range of the top note components should be from 0.1 mm/Hg up to 2.0 mm/Hg at 25.degree. C. PA1 (i) sodium stearate; PA1 (ii) bis(ureido) gels as disclosed in Freemantle in the article "Durable Organic Gels" appearing in CHEMICAL & ENGINEERING NEWS, Volume 76, No. 4, at pages 35-38, the disclosure of which is incorporated by reference herein. PA1 (iii) soap, fatty acid-based gelling agents as particularly described in U.S. Pat. No. 5,585,092 issued on Dec. 17, 1996 (Trandai, et al), the specification for which is incorporated by reference herein, including salts of fatty acids containing 12 to about 40 carbon atoms, preferably salts of C.sub.12 -C.sub.22 fatty acids, more preferably salts of C.sub.14 -C.sub.20 fatty acids and most preferably salts of C.sub.16 -C.sub.20 fatty acids with the salt forming cations for use in these gelling agents including metal salts such as alkalai metals, for example, sodium and potassium and alkaline earth metals, for example, magnesium and aluminum; and in addition, hydrogel-forming polymeric gelling agents as disclosed in U.S. Pat. No. 4,076,663 (Masuda, et al) issued on Feb. 28, 1978, the specification is incorporated by reference herein; and U.S. Pat. No. 4,731,067 (Le-Khac) issued on Mar. 15, 1988, incorporated by reference herein in its entirety. The suitable hydrogel-forming polymeric gelling agents are specifically discussed at columns 6-12 of U.S. Pat. No. 5,585,092 (Trandai, et al) issued on Dec. 17, 1996, incorporated by reference herein in its entirety; and PA1 (iv) silicone gels having the structures: ##STR16## PA1 water; PA1 propylene glycol; PA1 aluminum chlorohydrate; PA1 dimethicone; PA1 sorbitol; PA1 cyclomethicone; PA1 dimethicone copolyol; PA1 ethyl alcohol; and PA1 fragrance. PA1 (1) an enhanced sensory impression of the fragrance due to the increased duration of its release from the surface of the woven or non-woven fabric (e.g., cotton towel), plywood or skin, for example; PA1 (2) an enhanced sensory impression of freshness and vibrance due to the increased duration of fragrance ingredients that make up the topnotes of the fragrance; and PA1 (3) triggered release of the fragrance from water soluble polymer films upon the addition of moisture. PA1 (i) mixing means for a composition comprising a solvent selected from the group consisting of water, ethanol and mixtures of water and ethanol (e.g. 50:50 mixtures) with a solvent-soluble polymer solute to form a polymer solution; PA1 (ii) downstream from said mixing means, blending means for dissolving a soluble fragrance substance in said polymer solution in order to form an aromatized polymer solution (for example, the homogenizer and/or rotor/stator high shear mixer, briefly described, supra, and described in the description of FIGS. 3C, 3D and 3E, infra); PA1 (iii) downstream from said blending means, coating means for uniformly applying said aromatized polymer solution to said substantially planar surface of said solid or said semi-solid support; and, optionally, PA1 (iv) downstream from said coating means, drying means for drying the coated polymer solution on said solid or said semi-solid support. The coating means of (iii) may be any applicator device well known to those having ordinary skill in the art, for example, a high pressure nozzle spraying means is preferred when the coating is effected onto the surface of a woven or non-woven fabric. The drying means, useful in the practice of our invention, can be any portable or stationary drying apparatus, such as that manufactured by the CONAIR.RTM. Corporation.
indicates that a long lasting fragrance is obtained when hydroxypropyl cellulose in an amount of from about 1 up to about 30% is added to ethanol or methanol previously containing polyvinylpyrrolidone in an amount of from about 1 up to about 60%. Then a fragrance material in an amount of from about 1 up to about 60% by weight is added to the resulting material and admixed. The resulting product is applied to a film or paper. The Japanese Published Application J9 0057-428 does not disclose a control release technology provided by our invention. The Published Japanese Application, furthermore, does not teach that an effective control release system requires that the fragrance element and the film forming polymer be chosen such that the film forming polymer permits the fragrance to molecularly diffuse into the environment surrounding the film at a permeation rate of from about 1.times.10.sup.-7 up to about 0.1 mg-mm/cm.sup.2 -minute in a sustained and control release manner.
Holzner, U.S. Pat. No. 4,803,195 issued on Feb. 7, 1989 discloses personal care compositions having deodorant or antiperspirant activity and containing in addition to an active deodorant or antiperspirant base, a perfuming base either in the form of an aqueous emulsion or in microecapsulated form. The perfume base of Holzner is combined with a film forming substrate and an emulsifying agent. The Holzner, U.S. Pat. No. 4,803,195 claims:
a. a solid film-forming substrate chosen from polyvinyl acetate, polyvinyl alcohol, dextrins, natural or modified starch, vegetable gums, pectins, xanthans, carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose and lipoheteropolysaccharides, and PA2 b. an emulsifying agent chosen from mono- or diglycerides of fatty acids, esters derived from the combination of fatty acids with sorbitol or a saccharide, or their alkoxylated derivatives, or an ester of tartaric, citric, ascorbic or lactic acid."
Holzner and Moulin, Canadian Patent No. 2,008,556, disclose a perfuming composition with deodorant or antiperspirant action for use in personal care compositions. The Holzner composition contains, in addition to an active deodorant or antiperspirant base, a perfuming base either in the form of an aqueous emulsion or in microencapsulated form, with the perfuming base being combined with a film-forming substrate and an emulsifying agent, and the composition being characterized in that the film-forming substrate contains polyvinylpyrrolidone. The film-forming substrate in the Holzner and Moulin patent can contain, other than polyvinylpyrrolidone, at least one compound chosen from polyvinyl acetate, polyvinyl alcohol, dextrins, natural or modified starch, vegetable gums, pectins, xanthanes, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose and lipoheteropolysaccharides.
The prior art teaches away from our invention. Holzner, U.S. Pat. No. 4,803,195 requires the presence of an emulsifying agent and the formation of a fragrance polymer emulsion that is subsequently spray dried or used in emulsion form. Our invention does not require an emulsion, is applicable to all products containing volatile solvents that are applied to surfaces and requires that the film forming polymer is an effective "barrier" to the fragrance or fragrance ingredient as determined by the "FRAGRANCE PERMEATION TEST" hereinafter defined and hereinafter described.
Thus, whereas the prior art discloses the usefulness of films formed from modified starches such as hydroxypropyl cellulose in conjunction with fragrance, films formed from modified starches such as hydroxy cellulose do not fall within the scope of our invention. Ethyl tiglate is a common fragrance ingredient and permeates through a film formed from hydroxypropyl cellulose at a rate equal to its evaporation rate as determined by the "FRAGRANCE PERMEATION TEST" described, infra. Thus, hydroxypropyl cellulose would not evolve from such film into the environment proximate to the film by means of molecular diffusion at a permeation rate of &lt;0.1 mg-mm/cm.sup.2 -min.
Israel Patent No. 91422 issued on Oct. 31, 1995 (assigned to Dento-Med Industries Inc.) discloses a stable oil-in-water emulsion characterized in that it contains 2-hydroxyethyl methacrylate homopolymer from which a non-gummy, hygroscopic, flexible and pliable thin layer which can be deposited on an epidermal surface can be made and which optionally contains a plurality of plasticizers each having a different solvency power for 2-hydroxyethyl methacrylate homopolymer thereby controlling the pliability of the layer of 2-hydroxyethyl methacrylate homopolymer. On page 14 of Israel Patent No. 91422, it is indicated that the thin layer is formed when a cosmetic formulation is deposited on an epidermal surface. Although at pages 21-23 of the Israel patent, a cosmetic formulation of Dento-Med discloses a number of possible ingredients, there is no mention and no implication of the use of fragrances therein such as those fragrances which can diffuse out of the membrane as is claimed in our invention.
Blakeway and Sauvage, U.S. Pat. No. 5,369,092 issued on Nov. 29, 1994, discloses novel odorant compositions comprising panthenol with a perfume concentrate and ethanol, whereby the addition of panthenol prolongs the diffusion of perfume materials from the skin. The panthenol, however, is different in kind rather than degree from the polymers used in film forming the fragrance-containing films of our invention and does not give rise to the unexpected, unobvious and advantageous results of the fragrance carrier system of our invention; and further, does not give rise to the fragrance substance evolving from the film into the environment proximate the film by means of molecular diffusion at a permeation rate of from about 1.times.10.sup.-7 up to about 0.1 mg-mm/cm.sup.2 -minute.
PCT Patent Application No. 97,/25018 published on Jul. 17, 1997 and assigned to Launceston, Ltd. of St. Peter Port, Guernsey, Channel Islands, discloses a scented nail polish which comprises:
where the weight ratio of resin:liquid perfume is from 2.5:1 down to 1:2.5. Examples of the resin component of the scented nail polish of PCT Patent Application No. 97/25018 are nitrocellulose, cellulose acetate, cellulose acetate-butyrate, ethyl cellulose, vinyl polymers, methacrylate polymers and acrylate polymers. PCT Patent Application No. 97/25018 does not expressly or implicitly disclose the fragrance control release system of our invention, whereby a fragrance substance is evolved from a polymeric film into the environment proximate said film by means of molecular diffusion at a permeation rate of from about 1.times.10.sup.-7 up to about 0.1 mg-mm/cm.sup.2 -minute in a sustained and controlled release manner as measured by the "FRAGRANCE PERMEATION TEST" described, infra.